Molecular assembly of polycyanoarenes with silver salts and synthesis of polycyclic aromatic hydrocarbonds

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Abstract

This dissertation encompasses the investigation of two distinct subjects. In the first
part, which is in the area of molecular self-assembly, the complexation of organonitrile aryl
compounds with three different types of silver (I) salts is examined in the solid state. The
assembly of 1-(2,2-dicyanovinyl)naphthalene with silver hexafluoroantimonate resulted in a
cationic 3D network. Complexation of 4-(2,2-dicyanovinyl)biphenyl with silver
tetrafluoroborate and hexafluoroantimonate from benzene generated two similar structures.
While the former displays a cationic 3D network, the latter is defined by cationic 2D sheets.
Complexation of 9-(2,2-dicyanovinyl)anthracene with silver hexafluoroantimonate from toluene
afforded a cationic 2D ribbon, and from benzene, it yielded cationic 2D sheets. These
complexes contained solvent bonded to their structures. However, the hexafluoroantimonate
ion is nonbonding. The crystal association of 1,4-bis(cyanovinyl)benzene with silver triflate from benzene
yielded neutral 2D sheets whose imperfect-rectangular macrocyclic arrangements are
interconnected on both sides by bridges of benzene. On the other hand, the assembly of 1,3-
bis(cyanovinyl)benzene with silver triflate from benzene afforded a neutral 3D network formed
by two interconnected rings. Solvent and triflate counterions are bonded in both complexes. In the second part of this dissertation, the focus was on the synthesis of four linear PAHs
containing a perylene center formed by the connection of two substituted fluoranthene units.
Our synthetic approach included the elaboration of fluoranthene building blocks (monomers),
followed by the coupling of the monomers resulting in dimers, and finally, ring closure of those
dimers, which form the target structures. All of the stages were monitored by mass
spectrometry, 1H NMR, and 13C NMR spectroscopy. Out of four dimers, only one successfully
underwent ring closure. The UV/Vis absorption and fluorescence spectra for the only obtained
target compoundevaluated in chloroform showed absorption bands at 318, 352, 518, 558, and
606 nm and emission bands at 615 and 667 nm. The fluorescence quantum yield at 558 nm was
φF = 0.21, and at 606 nm was φF = 0.4. Since the differentiation between the targets relies on
the substitution pattern, these results suggest that changes in the fluoranthene moiety render
changes in the reactivity through the coupling reaction.